CN106932528A - The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl - Google Patents
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl Download PDFInfo
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- CN106932528A CN106932528A CN201511021474.5A CN201511021474A CN106932528A CN 106932528 A CN106932528 A CN 106932528A CN 201511021474 A CN201511021474 A CN 201511021474A CN 106932528 A CN106932528 A CN 106932528A
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- catalyst
- hydrolyzate
- ethyoxyl
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/68—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using high frequency electric fields
Abstract
A kind of analysis method of the chlorine vanadyl catalyst molecule formula being modified the present invention relates to ethyoxyl, including：The hydrolysis of catalyst；The measure of chlorine ion concentration [V] in catalyst hydrolyzate；The measure of vanadium ion concentration [V] in catalyst hydrolyzate；Modified chlorine vanadyl catalyst molecule formula (EtO) of ethyoxyl to be measured is determined by formula m=3- [Cl]/[V]mCl3-mVO.Ethoxyl content in the modified chlorine vanadyl catalyst of ethyoxyl can accurately be determined by the present invention, the modified catalyst molecular formula for being drawn can determine the ethoxyl content in the modified vanadium catalyst of ethyoxyl close to actual value currently without a kind of method of shaping.
Description
Technical field
The present invention relates to a kind of analysis method of ethoxyl content in vanadium series catalyst, more particularly to a kind of ethoxy
The analysis method of the modified chlorine vanadyl catalyst molecule formula of base.
Background technology
In the EP rubbers development of more than 40 years, the catalyst system and catalyzing of EP rubbers is constantly updated, from
The vanadium series catalyst and Titanium series catalyst of Ziegler-Natta (Z-N) catalyst system and catalyzing, to 90 years 20th century
The metallocene catalyst that grows up of generation, then to 21 century emerging non-metallocene catalyst.Catalyst is not
The disconnected direction towards high catalytic activity and high stability is gradually developed, make the performance of product and kind towards
More excellent direction is developed.
UCC companies of the U.S. are developed with SiO on gas-phase process2It is the basis of the vanadium series catalyst of carrier
On, the composite catalyst of Ti-V and Zr-V double activity center is developed, the composite catalyst can produce phase
To molecular vibrational temperature (Mw/Mn) curve in broad peak/bimodal polyethylene (PE) product.BP companies VC13
It is deposited on spherical MgC12On carrier be obtained vanadium series catalyst, with gas-phase process produce product not only
Mw/Mn (8~l0) is wider, and with preferable form, catalytic efficiency is also higher.Lukasz is equally used
Sol-gel process synthetic vectors, and supported V OC13Vanadium system PE catalyst is made, while using a chlorine two
Aluminium ethide modified catalyst, catalyst activity is carried to 25.8kg/mol by 7.8kg/mol.Russian Academy Of Sciences
The Bao Liesi Ke Fu catalyticing research spherical MgC1 of institute2It is vanadium series catalyst prepared by carrier, for slurry process
Vinyl polymerization, the polymer Mw/Mn of production is wide, melt flow rate (MFR) is adjustable, apparent density is high.
Ziegler-Natta type solution polymerization process is the conventional method for producing the minor official glue of second third, is that both can dissolve
Product, the homogeneous reaction carried out in the solvent that monomer and catalyst system are can dissolve again.Generally with linear paraffin
If n-hexane is solvent, vanadium oxytrichloride half as much again alkyl aluminium halide is catalyst, with hydrogen or other compounds
Used as molecular weight regulator, polymerization temperature is 30 DEG C~60 DEG C, and polymerization pressure is 0.4MPa~0.8MPa.
The main recovery by raw material preparations, polymerization, catalyst removal, monomer and solvent of technical process, refine, it is solidifying
The operation composition such as poly- and dry.Wherein typical manufacturer mainly has Dutch DSM N. V., the U.S.
ExxonMobil companies, Uniroyal companies of the U.S. (Lion companies of the Xian Ming U.S.), U.S. DuPont Dow
Elastomer company, Mitsui chemical company and Japan SYnthetic Rubber Co. Ltd etc..The production of each manufacturer
Technique differs from one another, wherein most typical representative is the solution polymerization process technique of DSM N. V., it is not only
Global maximum EP rubbers manufacturer, and it is poly- using solution in the device of Holland, Japan, Brazil etc.
Legal to be produced, its production capacity accounts for the 20% of world's solution polymerization process total productive capacity.
In recent years, DuPont Dow elastomers company developsTechnique successful Application industrially
For EP rubbers production brings important breakthrough.Technique uses metallocene as catalyst, highly concentrated
Synthesizing new EP rubbers in degree solution environmental.The technique is realized glues to relative molecular mass distribution, Mooney
The precise control of degree, ethene and ENB content, the rheological characteristic of rubber and curingprocess rate etc., so that
Realize the control to product uniformity.Polymerisation is carried out under the conditions of 120 DEG C, 3.4MPa.The work
Skill uses high temperature solution polymerization, uses the Titanocene catalyst system of constrained geometry, polymer quality
, up to 16.4%, catalyst residual quantity is considerably less in product for fraction, it is not necessary to which removing is processed, and invests low, produces
Product relative molecular mass distribution is narrow, and the length of polymer chain is uniform, and bulk density is small, and viscosity is high, DDGS
Content is low, can use sulfur cross-linking, external form when its molded mobility, tensile strength, calendering formation
The performances such as rate of extrusion when performance and extrusion molding are superior to traditional Ziegler-Natta types the third rubber of second
Sol solution polymerization technique, product Mooney range of viscosities is 20~45.
At present, the main initiator that EP rubbers synthesizer in the whole world is used has vanadium oxytrichloride, modified trichlorine
Vanadyl, metallocene.From polymerization methodses, due to efficiency of initiation, the difference of catalyst system and catalyzing, solution can be used
The modes such as polymerization, gas-phase polymerization.Jilin Petrochemical company EP rubbers device uses vanadium oxytrichloride to be catalyzed
Agent (abbreviation V- catalyst) and vanadium oxytrichloride add the ethyoxyl dichloro vanadyl that absolute ethyl alcohol reaction is prepared into urge
Agent (abbreviation Vx- catalyst), for producing straight chain EP rubbers product.
The content of the invention
Present invention aim at the analysis for providing a kind of modified chlorine vanadyl catalyst molecule formula of determination ethyoxyl
Method, this method can accurately determine the content of ethyoxyl in modified vanadium catalyst, so as to more be convenient to grind
Study carefully research of the catalyst to properties of product.
To realize the purpose of the present invention, the present invention discloses a kind of modified chlorine vanadyl catalyst molecule formula of ethyoxyl
Analysis method, including following process：
(1) hydrolysis of catalyst：
Chlorine vanadyl catalyst (EtO) that ethyoxyl is modifiedmCl3-mVO is slowly added under airtight condition
It is then closed to be kept for 30~120 minutes in 20~60mL deionized waters, obtain catalyst hydrolyzate；
(2) in catalyst in hydrolyzate chlorine ion concentration determination：
With phenolphthalein as indicator, gained catalyst hydrolyzate in step (1) is taken, use NaOH standard liquids
Titrated, the volume according to the NaOH standard liquids consumed when reaching titration end-point calculates catalysis
The concentration [Cl] of the chlorion in agent hydrolyzate；
(3) in catalyst in hydrolyzate vanadium ion concentration determination：
The another middle gained catalyst hydrolyzate of step (1) that takes is diluted, and obtains catalyst hydrolyzate dilution；
Using the ion of v element in inductive coupling plasma emission spectrograph measurement catalyst hydrolyzate dilution
Emission spectrum, according to its spectral intensity, with working curve method determine vanadium in catalyst hydrolyzate dilution from
Sub- concentration [V1]；According to extension rate, by the vanadium ion concentration [V in catalyst hydrolyzate dilution1] calculate
The vanadium ion concentration [V] gone out in catalyst hydrolyzate；
(4) determination of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl：
By the concentration [V] and chlorine of vanadium ion in the catalyst hydrolyzate of gained in step (2) and step (3)
The concentration [Cl] of ion calculates modified chlorine vanadyl catalyst molecule formula (EtO) of ethyoxylmCl3-mVO, wherein
The computing formula of m is m=3- [Cl]/[V].
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl of the present invention, wherein, step
(1) consumption of deionized water described in is preferably 20~40mL.
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl of the present invention, wherein, step
(1) time of closed holding described in is preferably 30~60 minutes.
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl of the present invention, wherein, step
(2) sampling amount of catalyst hydrolyzate described in is preferably 10mL.
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl of the present invention, is preferably applied to
The analysis of modified vanadium oxytrichloride catalyst molecule formula, further preferably urges suitable for alkoxy-modified vanadium oxytrichloride
The analysis of agent molecular formula.
The present invention has the advantages that：(1) ethyoxyl contains in can accurately determining modified vanadium catalyst
Amount；(2) the modified catalyst molecular formula for being drawn by the present invention is close to actual value；(3) currently without one
The method of kind shaping can determine the ethoxyl content in modified vanadium catalyst.
Brief description of the drawings
Fig. 1 is the working curve of the concentration of vanadium ion in determination catalyst hydrolyzate dilution in embodiment 1
Figure.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is premised on technical solution of the present invention
Under implemented, give detailed implementation method and process, but protection scope of the present invention be not limited to it is following
Embodiment, the technological parameter of unreceipted actual conditions in the following example, generally according to normal condition.
Embodiment 1：
20mL deionized waters are moved into through nitrogen so that the speed of 20r/s is slow with peristaltic pump at ambient temperature
Process and in closed 150mL triangular flasks, it is to be measured modified to extract 0.5mL with the syringe through dried process
Vanadium catalyst, is slowly dropped in the triangular flask equipped with deionized water, and time for adding was controlled at 1~2 minute
It is interior, with the carrying out being added dropwise, white haze rise is had in triangular flask, white haze is to dissociate the HCl gases for coming,
But continuity over time, HCl gases can be absorbed to form hydrochloric acid solution by deionized water, liquid table is observed
The aerosol situation in face, will now keep closed good.After 20min, exist without visual aerosol in bottle, now
Bottle stopper is opened, during hydrolyzate moved into 250mL volumetric flasks, constant volume is standby.
0.01mol/mL NaOH standard liquids, addition are added in alkaline buret>30mL, static reserve.
Then the modified vanadium catalyst hydrolyzates of 10mL are removed from above-mentioned 250mL volumetric flasks with 10mL pipettes,
It is placed in iodine flask, it is standby, so repeat to take out 3 hydrolyzate samples, to ensure the collimation of titration.
To 1 drop phenolphthalein solution is separately added into three iodine flasks, left hand controls the flow of alkali lye, and the right hand is gently
Shake iodine flask, to ensure the harmony of acid-base reaction.When pink colour is shown slightly in iodine flask, stop titration,
Bottle is shaken gently for, treats that pink colour disperses, then instill half drop alkali lye, be shaken gently for bottle, and rushed with distilled water
Pink colour disperses quickly in brush bottle wall, such as bottle, continues to instill half drop alkali lye, repeats aforesaid operations, treats powder in bottle
When color can not disperse completely, indicate that terminal has been arrived in this titration, write down the alkali lye consumption of consumption, such as table 1
It is shown.
The titration data table of table 1
The preparation of standard liquid：3 100mL volumetric flasks are taken, as shown in table 2, aluminium vanadium is separately added into and is mixed
Standardization solution (wherein vanadium ion concentration is (100 ± 1mg/L)), and 100mL is settled to respectively,
It is stand-by and be settled to 100mL respectively, it is stand-by.
The standard liquid of table 2
| Aluminium vanadium mixed standard solution volume V/mL | Correspondence vanadium ion concentration/(μ g/mL) |
| 1.0 | 1 |
| 5.0 | 5 |
| 10 | 10 |
The drafting of working curve：Inductive coupling plasma emission spectrograph is lighted a fire after start preheating 4h,
Stabilization 30min, rectifies an instrument, and instrument is adjusted to optimum Working, selects element to be measured and analysis wavelength,
The μ g/mL (water) of sequential determination 0；1.0μg/mL；5.0μg/mL；10 μ g/mL standard liquids, with vanadium from
Sub- concentration is abscissa (unit：μ g/mL), corresponding the intensity of spectral line be ordinate, drawing curve,
Its equation of linear regression is [V1] '=6.163479 × 10-3× I-0.1025682, linearly dependent coefficient
R=0.99999, wherein [V1] ' is the vanadium ion concentration (unit in solution to be measured：μ g/mL), I is catalysis
The intensity of emission spectra that agent hydrolyzate dilution is measured.
It is another to take catalyst hydrolyzate 1mL, and diluted 1000 times, catalyst hydrolyzate dilution is obtained,
Catalyst hydrolyzate is determined while using inductive coupling plasma emission spectrograph drawing curve
The v element emission spectrum of dilution.The vanadium in catalyst hydrolyzate dilution can be obtained according to working curve
Ion concentration [V1] ' (unit：μ g/mL), its unit is converted, obtain catalyst hydrolyzate dilution
Middle vanadium ion concentration [V1] (unit：Mol/L it is) 1.76 × 10-6mol/L.According to formula [V]=1000 [V1],
The concentration [V] for calculating vanadium ion in catalyst hydrolyzate is 1.76 × 10-3mol/L。
By the molecular formula (EtO) of the chlorine oxygen alkane catalyst that is modifiedmCl3-mVO draws the calculating of following ethoxyl content
Formula：
M=3- [Cl]/[V]
The concentration of vanadium ion, mol/L wherein in [V]-above-mentioned catalyst hydrolyzate；
Chlorine ion concentration in [Cl]-above-mentioned catalyst hydrolyzate, mol/L；
It is 1.26 to calculate the value of m, and the accurate formula for drawing catalyst to be measured is (EtO)1.25Cl1.75VO。
Claims (5)
1. a kind of analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl, including following process：
(1) hydrolysis of catalyst：
Chlorine vanadyl catalyst (EtO) that ethyoxyl is modifiedmCl3-mVO is slowly added under airtight condition
It is then closed to be kept for 30~120 minutes in 20~60mL deionized waters, it is transferred to 250mL volumetric flasks
In, constant volume obtains catalyst hydrolyzate；
(2) in catalyst hydrolyzate chlorine ion concentration measure：
With phenolphthalein as indicator, gained catalyst hydrolyzate in step (1) is taken, use NaOH standard liquids
Titrated, the volume according to the NaOH standard liquids consumed when reaching titration end-point calculates catalysis
The concentration [Cl] of the chlorion in agent hydrolyzate；
(3) in catalyst hydrolyzate vanadium ion concentration measure：
The another middle gained catalyst hydrolyzate of step (1) that takes is diluted, and obtains catalyst hydrolyzate dilution；
Using the ion of v element in inductive coupling plasma emission spectrograph measurement catalyst hydrolyzate dilution
Emission spectrum, according to its spectral intensity, with working curve method determine vanadium in catalyst hydrolyzate dilution from
Sub- concentration [V1]；According to extension rate, by the vanadium ion concentration [V in catalyst hydrolyzate dilution1] calculate
Go out vanadium ion concentration [V] in catalyst hydrolyzate；
(4) determination of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl：
By the concentration [V] and chlorine of vanadium ion in the catalyst hydrolyzate of gained in step (2) and step (3)
The concentration [Cl] of ion calculates modified chlorine vanadyl catalyst molecule formula (EtO) of ethyoxylmCl3-mVO, wherein
The computing formula of m is m=3- [Cl]/[V].
2. the analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl as claimed in claim 1,
Characterized in that, the consumption of deionized water described in step (1) is 20~40mL.
3. the analysis side of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl as claimed in claim 1 or 2
Method, it is characterised in that the time of closed holding described in step (1) is 30~60 minutes.
4. the analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl as claimed in claim 1,
Characterized in that, the sampling amount of catalyst hydrolyzate described in step (2) is 10mL.
5. the analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl as claimed in claim 3,
Characterized in that, the sampling amount of catalyst hydrolyzate described in step (2) is 10mL.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111830197A (en) * | 2020-07-14 | 2020-10-27 | 宁波拓烯新材料科技有限公司 | Method for analyzing composition of chlorine-containing vanadium compound |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3173903A (en) * | 1960-08-25 | 1965-03-16 | Hercules Powder Co Ltd | Copolymers of ethylene and propylene |
| US4259468A (en) * | 1978-08-17 | 1981-03-31 | Mitsui Petrochemical Industries Ltd. | Ethylene-α-olefin-polyene rubbery terpolymer and process for production thereof |
| CN85108908A (en) * | 1984-12-12 | 1986-08-06 | 埃克森研究工程公司 | Polymerizing catalyst and its preparation and application |
| CN1134710A (en) * | 1994-07-08 | 1996-10-30 | 蒙特尔技术有限公司 | Components and catalysts for the polymerization of olefins |
| CN1254720A (en) * | 1998-11-19 | 2000-05-31 | 恩尼彻姆公司 | Vanadium knid of catalysts, preparing process thereof and their application in polymerization (or copolymerization) of alpha-olefin |
| JP2004243197A (en) * | 2003-02-13 | 2004-09-02 | Japan Science & Technology Agency | Polymer fixed vanadium catalyst, production method therefor, and oxidization method |
| CN102827319A (en) * | 2012-09-07 | 2012-12-19 | 中国科学院长春应用化学研究所 | Vanadium catalyst and preparation method of vanadium catalyst as well as preparation method of ethylene-propylene copolymer |
| CN102964375A (en) * | 2012-11-28 | 2013-03-13 | 中国科学院长春应用化学研究所 | Vanadium catalyst, vanadium catalyst composition and preparation method of ethylene propylene rubber |
| CN103314017A (en) * | 2010-12-27 | 2013-09-18 | 维尔萨利斯股份公司 | Solid catalyst component, catalyst comprising said solid component, and process for the (co)polymerization of alpha-olefins |
-
2015
- 2015-12-31 CN CN201511021474.5A patent/CN106932528A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3173903A (en) * | 1960-08-25 | 1965-03-16 | Hercules Powder Co Ltd | Copolymers of ethylene and propylene |
| US4259468A (en) * | 1978-08-17 | 1981-03-31 | Mitsui Petrochemical Industries Ltd. | Ethylene-α-olefin-polyene rubbery terpolymer and process for production thereof |
| CN85108908A (en) * | 1984-12-12 | 1986-08-06 | 埃克森研究工程公司 | Polymerizing catalyst and its preparation and application |
| CN1134710A (en) * | 1994-07-08 | 1996-10-30 | 蒙特尔技术有限公司 | Components and catalysts for the polymerization of olefins |
| CN1254720A (en) * | 1998-11-19 | 2000-05-31 | 恩尼彻姆公司 | Vanadium knid of catalysts, preparing process thereof and their application in polymerization (or copolymerization) of alpha-olefin |
| JP2004243197A (en) * | 2003-02-13 | 2004-09-02 | Japan Science & Technology Agency | Polymer fixed vanadium catalyst, production method therefor, and oxidization method |
| CN103314017A (en) * | 2010-12-27 | 2013-09-18 | 维尔萨利斯股份公司 | Solid catalyst component, catalyst comprising said solid component, and process for the (co)polymerization of alpha-olefins |
| CN102827319A (en) * | 2012-09-07 | 2012-12-19 | 中国科学院长春应用化学研究所 | Vanadium catalyst and preparation method of vanadium catalyst as well as preparation method of ethylene-propylene copolymer |
| CN102964375A (en) * | 2012-11-28 | 2013-03-13 | 中国科学院长春应用化学研究所 | Vanadium catalyst, vanadium catalyst composition and preparation method of ethylene propylene rubber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111830197A (en) * | 2020-07-14 | 2020-10-27 | 宁波拓烯新材料科技有限公司 | Method for analyzing composition of chlorine-containing vanadium compound |
| CN111830197B (en) * | 2020-07-14 | 2022-08-02 | 拓烯科技(衢州)有限公司 | Method for analyzing composition of chlorine-containing vanadium compound |
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